JOURNAL OF

COMPOSITE
Article M AT E R I A L S

Journal of Composite Materials

0(0) 1–20
The effect of equal-channel angular ! The Author(s) 2020
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pressing (ECAP) on the properties [Link]/journals-permissions
DOI: 10.1177/0021998320979040
of graphene reinforced aluminium [Link]/home/jcm

matrix composites

€
Omer Güler1 , Nihal Ba
gcı1, Seval Hale Güler1,
Canan A Canbay2, Hasan Safa1, Taha A Yılmaz3 and
Mustafa Taşkın1

Abstract
In the present study, graphene nanosheets were synthesised by liquid phase exfoliation process, and the obtained
graphene was reinforced in the rates of 0.1, 0.2, 0.3 and 0.6 wt.%. After the composites were characterised, they
were exposed to Equal Channel Angular Pressing (ECAP) process. While 0.1 wt.% and 0.2 wt.% graphene reinforced
composite samples successfully completed the ECAP process, 0.1 wt.% and 0.2 wt.% graphene reinforced composite
samples were broken during the ECAP process. Electrical, thermal, and mechanical properties of the composite
increased with the increased amount of graphene. The mechanical properties of ECAP-processed samples showed
significant increases compared to non-ECAP processed samples. To figure out the effect of the ECAP process, moulds
with different channel angles were used, the ECAP temperature was changed, and different passes were performed and
the angles of 120
and 90
were used. ECAP-processed samples in both mould angles showed similar mechanical
properties. With the increasing ECAP temperature, the mechanical properties of the sample decreased, but its electrical
conductivity increased. As the number of passes increased, mechanical properties increased and crack formation in
material increased. In addition, it was not possible to successfully remove the matrix composites containing more than
0.3 wt.% graphene from the ECAP process. Especially in the sample containing 0.6 wt.% graphene, brittle fractures were
seen during the ECAP process and the sample was divided into many parts. The results showed that the composite
responded better to the ECAP process when low amounts of graphene were reinforced in the al matrix. Significant
improvements were observed in the properties of these composites after the ECAP process. In this study, the prop-
erties of composites with and without ECAP process were extensively investigated. The results were compared in detail
with the previous studies. The graphene was produced using a simple method and it was reinforced with the Al matrix
with the easiest possible method.

Keywords
Graphite, graphene, exfoliation, aluminium, powder metallurgy, equal channel angular pressing (ECAP)

Introduction
Graphene is formed by sp2 hybridization of regular
1
carbon atoms in the hexagonal structure.1 Metalurgical and Material Engineering Dept., Mersin University, Mersin,
Turkey
Two-dimensional, single layer nanoparticle has 2
Physics Dept., Firat University, Elazig, Turkey
attracted a great attention due to its excellent proper- 3
Metalurgical and Material Engineering. Dept., Ataturk University,
ties such as Young’s modulus (1 TPa),2 fracture Erzurum, Turkey
strength (130 GPa),3 and thermal conductivity
(5000 Wm1K1). Graphene nanosheets (GNSs) made
Corresponding author:
€
Omer Güler, Engineering Faculty, Metalurgical and Material Eng. Dept.,
up of several graphene layers have similar properties Mersin University, Post Code: 33110, Mersin, Turkey.
with single layer graphene.4,5 Therefore, graphene is an Email: oguler@[Link]
2 Journal of Composite Materials 0(0)

ideal second phase to improve mechanical, electrical some conditions. There are many different SPD proc-
and thermal properties of metals,6 ceramics7 and poly- essing methods such as high-pressure torsion (HPT),34
mers8 simultaneously. These new composites can torsion extrusion (TE),35 accumulative roll-bonding
be applied in different fields including lithium-ion (ARB),36 and equal-channel angular pressing
batteries,9 biosensors,10 transparent conductors11 and (ECAP). However, the most striking method is the
supercapacitors12 and many other fields.13 When equal-channel angular pressing developed by Segal.
compared to the one-dimensional carbon nanotube, It has several advantages; firstly, setting up and using
two-dimensional graphene is easy to control and scat- an ECAP mould is relatively easy. Repeated pressing of
ter within the metal matrix. It has been assumed that the same sample is possible. It can be applied through
GNSs can perform significantly better than carbon development of multi-pass moulds, rotary moulds or
nanotubes (CNT) and they can have a great potential side extrusion plants. ECAP samples can be easily
as ideal reinforcement in composite materials. scaled to produce relatively large cast materials
Therefore, investigating and developing GNS rein- having the potential to be used in various applications
forced nanocomposites are important for practical from biomedicine to aviation and aerospace industries.
applications of graphene. In addition, two factors can A relatively short rod or a sample in the form of a rod
be mentioned that make GNSs an ideal reinforcement is pressed through a mould constrained in a channel
in metal matrix composites (MMC). These are the fact bent at a sharp angle.37–40 In application, ECAP is seen
that; 1) GNSs exhibit similar properties with graphene, to have more benefits than HPT. The reason is that
2) graphite can be produced in large quantities by since high tensions are obtained in a single pass from
chemical exfoliation.4,14 ECAP mould and multiple passes are also provided,
There are various methods for graphene production. there is a potential to grow the process for industrial
Epitaxial growth on SiC,15 chemical vapor deposition applications. The ECAP principle is the deformation of
(CVD),16 liquid-phase exfoliation (LPE),17 reduction
a metal through a simple cutting process. Cutting pro-
of graphene oxide,18 and hybrid methods using the
cess occurs without any change in cross-sectional area
combination of several methods19,20 can be given as
of the sample.41–43
examples for these methods. Graphene can be pro-
In ECAP, a sample is pressed through a mould in
duced not only from an inexpensive and abundant
which two channels with equal cross section intersects
source (graphite) but also using various low-cost meth-
at U angle and another W angle defines the curvature
ods. The liquid-phase exfoliation of graphite is the
arc at the outer point of the intersection point of the
most widely used method for industrial production of
two channels. Samples are generally circular or square-
small graphene sheets.21–24
shaped depending on the sizes of the channels. After
Studies conducted on the synthesis of graphene rein-
applying appropriate lubricant materials, the sample is
forced metal matrix composites have mainly focused on
graphene-copper, graphene-magnesium and graphene- placed in the input channel. Then, by using a punch
Al composites.25–27 Among them, aluminium matrix under pressure, it is extruded from the exit channel.
composites (AMC) have become a highly attractive The deformation mode in ECAP process is a simple
material group due to their remarkable physical and cutting. There are four main routes in ECAP.44,45
mechanical properties such as low thermal expansion, There are no turns on route A. In route C, the
high specific modulus, good wear resistance and light sample turns 180
after each pass. In the routes BA
weight.28 Various studies have been conducted on this and BC, a turn with 90
is applied in an alternative
matter.4,14,29 Compared to pure aluminium, many direction and in the same direction between successive
studies have been conducted by using Al as a matrix passes. Process route affects grain refinement and grain
material by weight due to its mechanical and physical shape significantly.38,46–48 Also, when ECAP is applied
properties and preferring graphene nanosheet as rein- to the materials, a few different factors affecting
forcing material.30–32 machinability affect the microstructural properties of
In the industry, there is an increasing demand for the pressed billets. Firstly, these factors are directly
the production of nanostructured materials with a high associated with the inner angle between channels (U)
performance/weight ratio such as Mg, Al and Ti-based and the outer angle (W) values by which the channels
alloys. Nowadays, one of the most popular and eco- intersect. Secondly, there are experimental factors such
nomical ways to produce nanostructured materials is as pressing speed, temperature of the pressing process
the severe plastic deformation (SPD) approach.33 and the presence or absence of any back pressure.
Processing metals by applying severe plastic deforma- Along with these, sliding systems, cutting models,
tion to composite materials has drawn a considerable total stress to be applied to the sample, mould geome-
attention due to the potential of obtaining grain refine- try and press regimes are the main experimental factors
ment in micrometre or even nanometre range under affecting ECAP. These parameters play an important
Güler et al. 3

role in microstructural refining during the pressing study, graphenes are produced successfully with a
process.49 simple method and Al was reinforced into the matrix
The correlation between U angle between channels with the easiest method possible. Although this com-
and W angle of the outer curvature arc where the two posite can be produced by using novel methods, these
channels intersect: (e) size of the effective load after N are small scale productions in laboratory scale. In this
passes is given with the following equation (1). study, the potential of transforming the preferred pro-
     duction methods into commercial production is quite
N ðU þ WÞ ðU þ WÞ high.
ðeeqÞ ¼ 2 cot þ W cosec
冑3 2 2
(1) Exprimental process

The size of e in the case where the sample is pressed Graphene production
once through the mould depends on U and W values In the production process, “h-graphite powder (99.5%,
through the correlation given in the equation when Merck) was used as the starting material. As seen in the
N ¼ 1. When U ¼ 90
and W ¼ 0
, total load becomes production scheme in Figure 1, hexagonal graphite
e ¼ 1.15 in the above equation. Small U provides powders were transformed into graphene nanosheets
higher cutting stress with each pass. It is therefore by using liquid phase exfoliation method. Here,
more effective in refining the grains. In the literature, Dimethylformamide (DMF) was used as the solvent.
U values varying between 90
and 157.5
have been In order to increase the efficiency of the obtained gra-
reported.40,50,51 phene, sodium dodecyl sulfate (SDS) was added as a
In this study, graphene production through liquid surfactant. For the graphene production in the study,
phase exfoliation method was successfully performed 0.7 gram graphite and sodium dodecyl sulfate (SDS)
and then Al was reinforced to the matrix. The proper- was sonicated in 100 ml Dimethylformamide (DMF)
ties of the obtained composites were investigated and at 75% power for 2 hours with the help of ultrasonic
then ECAP was applied to these composites and the homogenizer (Sonics Vibra-cell VCX 750). It was then
changes in their properties were examined. In this subjected to centrifuge process for 3 hours at 6000 rpm

Figure 1. Graphene production scheme.

4 Journal of Composite Materials 0(0)

Figure 2. Nanocomposite production process.

in a centrifuge device (Hermle Z 206 A). The product 600
C under Argon atmosphere. In order for the sin-
separated from the solvents used was washed. The tered samples to reach full density, they were cold
obtained samples were subjected to Transmission pressed again at 500 MPa and 2nd sintering process
Electron Microscope (TEM) (JEOL JEM-1011), was applied at 600
C for 2 hours.
Raman Spectroscopy (WITech alpha 300 R), X-ray pho- In the study, a mould with channel angle ¼ 120
and
toelectron spectroscopy (XPS) (Specs-Flex) analysis. corner angle ¼ 20
was worked in BC route. ECAP pro-
cess was applied to the graphene reinforced composites
Production of aluminium matrix graphene reinforced produced with powder metallurgy method and to the
composites and their ECAP process pure aluminium samples. It was aimed to reveal the
changes that may occur on the material without any
In the study, the produced graphene of 0.1, 0.2, and change in the dimensions of the materials with 20-mm
0.3 wt.% was added into the aluminium matrix. As diameter. First of all, the mould was heated at 200
C
seen in the nanocomposite production scheme in for 1 hour. Then, after the sample was placed and
Figure 2, appropriate rate of graphene was added heated for a short time, the ECAP process was con-
into 105 ml ethanol and sonicated for 15 minutes with ducted with 120
mould angle at 200
C. It was pressed
an ultrasonic homogenizer. After homogeneously dis- with a pressure of 100 MPa, a speed of 0.025 mm/sec
tributing the graphenes in the ethanol, 45 g Al powder and without any back-pressure application. It was then
was added. After the alcohol evaporated in the mag- left to cool down at room temperature (Figure 3).
netic stirrer, the milling process was performed in order Cracks occurred in the 0.3% graphene reinforced com-
to increase the homogeneous distribution rate of gra- posite sample after the process, which prevented the use
phene into the Al matrix in ball mill (Retsch PM100). of the sample. For these reasons, ECAP process could
The powders were subjected to milling process in a be applied to only 3 groups of samples in a proper way.
hardened steel vial with 250 ml capacity, using a These are pure Al, 0.1% graphene reinforced, and
12-mm-diameter ball in 15:1 powder ball ratio at 0.2% graphene reinforced composites.
170 rpm for 45 minutes. After the milling process, Table 1 shows information about the produced sam-
bulk samples were obtained by cold pressing at ples and the codes given to the samples.
500 MPa pressure in press moulds. The obtained sam- The internal structure examination of the
ples were subjected to sintering process for 2 hours at composite materials with and without ECAP process
Güler et al. 5

Figure 3. Image of equal-channel angular pressing (ECAP).

Table 1. The percentage of powders and experimental conditions to be used in the experiment.

Samples Graphene (% wt.) ECAP ECAP conditions

N0 0 unperformed –
N1 % 0.1 unperformed –
N2 % 0.2 unperformed –
N3 % 0.3 unperformed –
N4 0 Performed (1 time) Mold angle 120
, process temperature 200
C
N5 % 0.1 Performed (1 time) Mold angle 120
, process temperature 200
C
N6 % 0.2 Performed (1 time) Mold angle 120
, process temperature 200
C
N7 0 Performed (1 time) Mold angle 90
, process temperature 200
C
N8 % 0.1 Performed (2 times) Mold angle 120
, process temperature 200
C
N9 % 0.1 Performed (4 times) Mold angle 120
, process temperature 200
C
N10 % 0.1 Performed (1 time) Mold angle 120
, process temperature 400
C

was carried out by using Scanning Electron Microscope test of the samples. The resistance values were mea-
(SEM) (Zeiss Supra 55) brand and model device. sured and electrical conductivity was calculated using
The samples were subjected to abrasive wear test by equations (2) and (3).
being exposed to different loads (10 N-20N-30N) at  
distances determined as 50 m, 100 m, and 150 m. A
SEM images were taken from the wear surfaces. q ¼ Rx (2)
L
Micro and macro hardness tests were applied to the
samples. For compression tests, (Shimadzu AG-X) 1
device was used. The electrical conductivity device r¼ (3)
q
(FYTRONIX) was used for electrical conductivity
6 Journal of Composite Materials 0(0)

Here, q is the resistivity ([Link]), r ([Link])1, R approximately 286 eV shows C-O bond. In XPS anal-
is resistance (ohm), A is the cross-sectional area of the ysis, the graphene obtained with DMF and SDS solu-
sample (cm2) and l is the length of the sample (cm). tion is seen to have C-C bond. This obtained peaks is
seen in the similar literature studies.52,53
Raman spectroscopy has emerged as a technique
Results and discussion with high efficiency for the characterization of most
The graphenes used as the reinforcing elements were materials. Graphene can be easily defined by Raman
produced using liquid phase exfoliation method. spectroscopy. It also allows to analyse of graphene
Figure 4 shows transmission electron microscopy layers and find their defects. For few-layered graphene
(TEM) images, X-ray photo electron spectroscopy (FG), there are three peaks at the values of 1350 cm1
(XPS) and Raman analysis of the obtained graphenes. (D peak),54 1580 cm1 (G peak)55 and 2714 cm1 (2 D
In the TEM image seen in Figure 4(a), the graphene peak). This result confirmed that the exfoliation
is seen in the marked area. The layers were overlapped method produced FG. However, it should not be for-
in some places and impurities were seen in the gotten that there are also multi layers graphenes
structure. together with FGs in the structure. The most promi-
X-ray photoelectron spectroscopy is one of the best nent Raman characteristics for graphite materials are
characterization methods for detecting the presence of the D-band associated with the defects in the layers at
oxides in graphene nanosheets, conducting elemental 1350 cm1, G-band associated with the vibration of
analysis and characterizing the quality of graphene carbon atoms showing sp2 hybridization at 1580 cm1
sheets. When XPS analysis in Figure 4(b) was exam- and 2 D-band associated with lattice vibration with two
ined, the binding energy of approximately 285 eV phonons at approximately 2700 cm1. Besides, the
shows C-C bonds and the binding energy of most important fingerprint of graphene is the peak

Figure 4. a) TEM image, b) XPS, c) Raman spectroscopy of the graphenes.

Güler et al. 7

point of 2 D band at 2700 cm1. In line with this of grains can be clearly seen. When other studies on
information, all peaks are seen in Figure 4(c). In the ECAP process were examined, it was seen that the
studies conducted for graphenes produced with exfoli- microstructure images taken as a result of the forming
ation method, DMF and SDS were found to be the best process showed similar characteristics and orientations
solvent and surfactant, respectively.56–59 with the current study.60–62
Graphenes reinforced into Al matrix are distributed Figures 7(e) and (f) show SEM images of the sample
in three ways in the matrix as given in Figure 5, 1) subjected to more than one ECAP processes. It can be
Graphene layers are embedded in the Al matrix in asserted that there was a decrease in the grain sizes with
some regions. This can be explained by the fact that the increasing ECAP number. Likewise, it is also clear-
graphene layers are embedded into the soft Al matrix ly seen that the porosities located on the surface due to
with ball impacts during the milling process. 2) In some powder metallurgy oriented towards the elongation of
regions, graphenes surround Al particles or grains. 3) the grains. It can also be asserted that the porosities
Agglomerated graphenes were seen in some regions of that did not show orientation formed on the surface
some samples with the increasing amount of graphene. while passing through the channel in ECAP process.
Microstructure examination of the produced gra- When the surface porosities forming during ECAP
phene reinforced Al matrix composites was performed were compared, the most surface porosity was
in SEM. Figures 6(a), (b), (c), (d), and (e) show SEM observed in the sample N7. Although N8 and N9 sam-
images of N0, N1, N2, and N3. When the non-ECAP ples were subjected to more ECAP cycles than N7
processed N0, N1, N2, and N3 samples were examined, sample, the only reason why porosities or cracks
it can be said that particles transformed from spherical formed more in N7 sample during ECAP was the use
form to plate form with the effect of milling process in of 90
mould during the ECAP of this sample. This
N0 sample. This situation that occurred with the effect situation is also mentioned in the literature. In fact,
of ball impacts, is due to the nature of the milling pro- although there is a significant difference in terms of
cess. With the increasing amount of graphene, graphe- mechanical properties of the samples obtained from
nes are seen to be more common in the matrix. 90
and 120
moulds among moulds used in ECAP
Graphenes shown by arrows are homogeneously dis- process applied to the sample or other characteristics,
tributed throughout the structure. Although there are higher amount of ECAP stresses are required in case of
still gaps in the structure, their number is very small. using a 90
mould. In addition, passing the sample
Figure 7 shows SEM images of the ECAP-processed through the channel with 90
angle increases the pos-
samples. The orientation of the grains in the samples sibility of cracking or fracture of the sample much
N4, N5, N6, N7, N8, and N9 was clearly seen. Besides, more. In fact, only pure Al sample was successfully
it was seen that the graphene layers were also oriented subjected to ECAP from the 90
mould in this study.
along with the grains because of a serious plastic defor- Fractures occurred in graphene reinforced samples.
mation such as ECAP. During the process, some Exfoliated structures formed on the surface of the
regions where micro cracks formed were found. This samples N8 and N9 as shown with arrows. Although
is due to the fact that micro gaps merge and transform these exfoliated structures were very similar with gra-
into a larger gap during plastic deformation. As stated phenes, their high thicknesses weakened this possibili-
above, it can be clearly seen that the grain sizes of the ty. Especially, the presence of these structures in the
samples were smaller and they were oriented. The inter- samples N8 and N9 suggested that Al particles sur-
esting thing here is that although the ECAP process rounded the graphene during ECAP process and they
was conducted over recrystallization temperature broke away from the surface with increasing stress.
(200
C), recrystallization was not observed in the While Figure 7(g) shows SEM image of the fracture
grains. Grain boundary separations and the orientation surface of the sample N9, Figure 7(h) shows the SEM

Figure 5. Distribution patterns of graphenes in Al matrix.

8 Journal of Composite Materials 0(0)

Figure 6. SEM image of a) N0, b) N1, c) N2, and d) N3 samples.

image of the fracture surface of the sample N10. As can If the graph of ECAP-processed pure and 0.1% gra-
be seen from these SEM images, fracture surfaces of phene reinforced Al composite materials having the
the ECAP-processed samples containing low amount codes of N4 and N5 shown in Figure 8(a) and (b)
of graphene were different. Graphenes embedded into was examined, it was observed that both microhard-
Al particles and oriented towards the direction of the ness and macrohardness values increased with the rein-
fracture. While graphenes were embedded on one side forcement of graphene. These results are consistent
of the separated surface, the other fracture side seemed with the literature.60,63–66 It was observed that there
fracture by being peeled off from the graphene. was a serious increase in the hardness of the ECAP-
Figure 8 shows microhardness and macrohardness processed samples. While microhardness value of the
test results of the Al matrix graphene reinforced sample N0 in Figure 8(a) was 34.6 HV, an increase of
composites with and without ECAP process. If we 33% was observed when the same sample was sub-
consider the non- ECAP processed samples given in jected to ECAP process. While microhardness value
Figure 8(a), it was observed that there was an increase of the sample N1 was 35.7 HV, an increase of 45%
up to 0.3% in microhardness values but there was a was observed after ECAP process. If the macrohard-
decrease in microhardness as the reinforcement rate ness values of these samples in Figure 8(b) were exam-
increased. The increase in microhardness of the com- ined, it was determined that there was increases of
posite with the increasing amount of graphene was 159% and 140% with the process of ECAP to the
an expected situation. The highest value was observed samples N0 and N1, respectively. The sample N6 was
in 0.3% graphene reinforced composite material. obtained by subjecting 0.2% graphene reinforced
This was estimated to be caused by the insufficient composite to ECAP process. Compared to the sample
reinforcement distribution in the matrix with N4, microhardness increase in this sample was over
increasing amount of graphene and the formation of 25%. Compared to the pure sample without ECAP,
agglomerates. this increase was above 50%. When the samples
Güler et al. 9

Figure 7. SEM images of a) the samples N4, b) N5, c) N6, d) N7, e) N8, f) N9, g) N9 (fracture surface), and h) N10 (fracture surface).

N4-N8-N9 were compared with each other, it was to ECAP process with 90
channel angle. All other
clearly seen that the hardness of the composite conditions were the same. As is seen, hardness value
increased significantly with the increasing number of of the sample subjected to ECAP process with 90

ECAP. Another result that should be noted here is channel angle was 10% higher compared to the
the correlation between the sample N4 and the sample subjected to ECAP process with 120
channel
sample N7. While the sample N4 was the pure Al angle. However, what should not be forgotten is that
sample subjected to ECAP process with 120
channel the possibility of cracking of the samples or more pre-
angle, the sample N7 was the pure Al sample subjected cisely, the possibility of being unable to pass the
10 Journal of Composite Materials 0(0)

decreased significantly with the increasing graphene.

This was associated with agglomeration and improper
distribution of reinforcement in Al matrix. Hardness
measurements of these samples were examined by
using Rockwell hardness test device. When the hard-
ness values were examined, it was found that the hard-
ness value of Al matrix composites containing 0.1%
and 1% graphene decreased compared to pure Al.67,68
Figure 9 shows electrical conductivity values of
the samples. Self-conductivity values of the materials
were found using equations (1) and (2). These self-
conductivity values were then transformed into %
IACS. % IACS (International Annealed Copper
Standard) is a conductivity measurement standard,
which is performed by accepting the self-conductivity
of fully annealed pure copper as 100% and 100% IACS
is 58 MSiemens/m.69
Figure 9(a) shows that the electrical conductivity
values increased with the increasing amount of rein-
forcement in Al-graphene nanocomposites without
ECAP process. While the electrical conductivity value
of pure Al (N0) was 26%, this rate increased to 55% in
the sample with 0.3% graphene reinforcement. Figure 9
(a) shows electrical conductivity values in ECAP-
processed Al-graphene nanocomposites. Electrical con-
ductivity value also increased along with the increasing
rate of graphene. The increasing electrical conductivity
with the increasing rate of graphene is an expected
situation. While the electrical conductivity value of
Figure 8. a) Microhardness of the samples with and without
ECAP process b) Macrohardness of the samples with and with-
the sample N0 was 26%, this value increased to 56%
out ECAP process. in N4 sample with ECAP process. this value which is
38% in the N1 sample increased to 65% in the sample
samples from the process from the mould with 90
N5 with the effect of ECAP.
channel angle increases. In fact, in this study, none of The reason why the electrical conductivities were
high in the ECAP-processed samples than the non-
the graphene reinforced samples could be successfully
ECAP processed samples was attributed to 2 reasons.
passed through the 90
mould, and the samples were
1) With the ECAP process, most of the gaps in the
broken in the mould. The sample N10 was the compos-
structure were removed or collected on the surface.
ite sample subjected to ECAP process with the 120

This caused an increase in conductivity. 2) Before
mould angle at 400
C. The increase in the process tem-
ECAP process, graphenes randomly distributed in the
perature caused the hardness of the sample to decrease. composite were oriented in the same direction, that is,
As mentioned before, the material recrystallised during in the direction of ECAP after the ECAP process. This
the process due to the very high process temperature caused an increase in electrical conductivity in that
and ECAP was not successful. direction. In particular, orienting graphenes in a certain
As seen in the macrohardness graph given in direction in order to increase electrical conductivity of
Figure 8(b), a continuous increase was observed with composites in copper-graphene composites is one of the
the increasing rate of reinforcement. This situation mostly studied subjects. Because of these reasons, there
shows similarities with the other literature studies.67,68 are numerous publications reporting significant
It is important to note that the graphene amount was increases in the electrical conductivity of the compo-
limited to 1 wt.% in the Al matrix in the present study. sites.70–73 As can be seen in Figure 9(a), the sample
This is because excessive amount of graphene in Al exhibiting the highest conductivity was the sample
matrix led to poor mechanical properties since it did N10. Subjecting this sample to ECAP process at
not show a good reinforcement distribution in the 400
C caused a high rate of recrystallisation in this
matrix. In addition, mechanical properties of compos- sample as mentioned in the previous section.
ite materials in the addition of graphenes over 1 wt.% Subjecting this sample to ECAP process caused the
Güler et al. 11

Figure 9. a) Comparison of the changes in electrical conductivity of the ECAP-processed and non-ECAP-processed samples b)
Comparison of electrical conductivity of the samples N4-N5 c) Comparison of electrical conductivity of the samples N0-N4-N7 d)
Comparison of electrical conductivity of the samples N0-N1-N4-N5.

pores resulting from production by powder metallurgy Figure 9(d) shows changes in the electrical conduc-
to disappear and graphenes to align in the same direc- tivity of the sample with 0.1% graphene reinforcement
tion as in the sample N5. The sample N10 showed after different ECAP processes. It was explained in
higher conductivity compared to the sample N5 since more detail that the sample N5 showed a higher con-
high ECAP temperature increased the recrystallisation ductivity than the sample N1. In this way, the point
rate and thus contained less defects compared to the that needs to be considered is that electrical conductiv-
sample N5. ity decreased with the increased number of ECAP.
In Figure 9(b), selecting the mould angle as 90
(N7) Carrying out one ECAP was very beneficial in terms
caused a decrease in electrical conductivity. The main of the sample produced with powder metallurgy to
reason for this situation is the micro cracks on the surface reach high densities and the graphenes to align in
due to the interaction between the sample and mould and ECAP direction. However, the decrease in the grain
due to very high stresses during the ECAP process. As size of matrix with the increasing number of ECAP
seen in Figure 9(c), electrical conductivity value of pure and increasing defects in the structure reduced the
Al composite subjected to ECAP was 56%; however, the mean free pathway of the electrons in Al and this
electrical conductivity value of the Al-graphene compos- caused a decrease in the conductivity compared to the
ite with 0.1% graphene reinforcement increased to 65%. sample subjected to ECAP once.
This showed that the electrical conductivity values The wear samples produced in this study were
increased after ECAP process in pure Al and Al compos- exposed to different loads (10 N-20N-30N) at deter-
ite with 0.1% graphene reinforcement. mined distances (50 m-100m-150m) and the specific
12 Journal of Composite Materials 0(0)

loss gradually decreased depending on the amount of

graphene reinforcements added into the material.74,75
This is due to the decreased friction coefficient with
increasing graphene amount due to the lubricating
properties of graphene. Besides, in general, softer mate-
rials have lower wear resistance than harder materials.
In the present study, hardness tests showed that the
strength of the composite increased with the increasing
amount of graphene. Thus, the lowest material loss was
observed in the sample N3 having the highest graphene
content. Additionally, it is known that the wear rates of
the samples also increase as the load increases.
Figure 11 shows the comparison of pure and 0.1%
graphene reinforced composites with and without
ECAP process for 50 m, 100 m, 150 m distances. Wear
resistance of pure Al (N0) was observed to increase as
expected after ECAP process (N4). The wear rates of
the samples also increased as the load increased. It was
determined in the graphs that the wear resistance was
increased after 0.1% graphene reinforced composite
(N1) sample was processed with ECAP (N5). These
results were confirmed when the literature studies
were reviewed.76 There were 2 reasons why the wear
resistance increased in samples with ECAP. 1) With
ECAP process, the grain refined in the samples, dislo-
cations increased and hardening occurred and thus
the wear resistance increased. 2) The wear resistance
increased due to the graphene reinforcement and the
orientation of graphenes in a certain direction with
ECAP.
Figure 12 shows optical images of the samples N0,
N1, N2, and N3 after wear. In the images given in
200 mm for each, traces indicating plastic deformation
on worn surfaces were observed for 10 N, 20 N, and
30 N load ranges. As shown in the figure, it was seen
that deeper grooves formed on the worn surfaces of the
sample N0, i.e. Al without reinforcement, through the
shear direction. A significant amount of plastic defor-
mation occurred on the worn surface with the increase
Figure 10. Specific wear rates of the composites for different of the applied load. On the other hand, various micro
loads and different wear distances. a) 50 meter, b) 100 meter, c)
and macro grooves were noticed in smaller sizes in the
150 meter.
graphene reinforced composites compared to Al with-
out reinforcement. Similar studies support this result.67
wear rates were calculated according to the equation (4).
Figure 13 shows optical and SEM images of N0, N1,
  N4 and N5 samples respectively for comparison.
wv
ws ¼ (4) Figure 13(a) shows grooves of N0 composite, crack
Vs F n
formation and wear marks of pure Al showing exfoli-
ation are seen. The surface of the wear scar revealed the
As expected in the graphs given in Figure 10, the formation of cracks. Since the sample is a pure and soft
wear resistance in the samples increased with the material, microcracks occurred due to the effect of
increasing rate of graphene. Here, non-ECAP- plastic deformation. These microcracks grow and
processed samples were considered. The sample with cause the separation of the surface layer. As a result,
the highest material loss was the sample N0, which parts ruptured from the material with high friction
was pure Al. This is because no additive material was coefficient and increasing wear rate. In the N1 compos-
added as reinforcement. If one looks closely, material ite given in Figure 13(b), the damage areas of plastic
Güler et al. 13

Figure 11. Comparison of wear values of the samples N0-N4 and N1-N5, a) for 50 meter, b) for 100 meter, c) for 150 meter.

deformation were smaller with the addition of 0.1% contact, thus causing friction coefficient and the wear
graphene. In addition, it is seen that this wear process rate to increase. However, this is less effective graphene
has typical grooves and there were white particles rup- reinforced composites compared to the other rein-
tured from the samples in SEM image. During the wear forced composites (reinforcements like ceramic).
process, graphene nanolayers separate and break Because the thermal conductivity of graphene is very
depending on the process dynamics. A film forms high and it conducts well the heat releasing during fric-
between the metal particles and contact due to wear tion. This causes the wear resistance to be more limited
process. In the literature studies, during the wear pro- compared to the other types of reinforcements.77,78
cess, the temperature at the interface increases in the When N4 and N5 composites were examined in
graphene-reinforced composite as a result of the Figures 13(c) and (d), the orientation of the grains
14 Journal of Composite Materials 0(0)

Figure 12. Optical microscope images of wear surfaces of a) N0, b) N1, c) N2, and d) N3 samples.

caused by the ECAP effect with severe plastic deforma- properties made it possible to use the alloy in various
tion was observed. The obtained images are also sup- engineering applications requiring high strength.81
ported by various studies. Gao et al., studied the Similarly, Bongale et al., determined that there was a
ECAP’s effect. They found that severe plastic deforma- significant amount of grain refinement in the samples
tion occurred with one pass during ECAP and after after each ECAP pass. It was reported that the grain
two-pass ECAP, the grain size of the alloy further size of the sample decreased from 75 mm to 36 mm after
reduced. The samples were subjected to a basically three passes from the ECAP mould.82 Wang et al.,
simple cut during ECAP. Boundaries with low angle found in their SEM study that the morphologies of
were cut with slip planes. Thus, a microstructure with the worn surfaces of all samples were reasonably sim-
wide angle borders formed. In conclusion, it was con- ilar. They indicated that all tested samples exhibited
cluded that the grain size decreased gradually with the exceptional wear with evidences such as very white
increase in the number of passes.79 Ramu et al., studied debris separated from the samples. The image of the
on Al-SiCp composites. They observed that significant worn surfaces of the samples was reported to be typical
grain refining occurred with the effect of ECAP.80 for soft and ductile materials such as copper, alumini-
Thiyaneshwaran et al., determined that the wear resis- um and gold.83
tance of the alloy increased after ECAE process. They In the studies conducted by Derakhshandeh et al.,84
attributed this to the formation of ultra-fine grains and and Chegini et al.,,85 the effect of ECAP was investi-
homogeneous distribution. It was found that the wear gated. They reported that there are some grooves due
mechanisms for the sample before ECAE and some to the high porosity in microstructure and the separa-
separated layers on the surface were abrasive. The sep- tion of material from the surface and plastic deforma-
arated layers were mainly caused by the cracks forming tion. They stated that the worn surfaces was composed
under the surface due to high plastic stress on the sur- of a combination of adhesion regions, plastic deforma-
face during the slip. Some grooves occurred due to tion bands in the slip direction and separated layers.
these separated layers on the surface. The growth of Similarly, all studies emphasized that the effect of
cracks was facilitated by defect or defects in the mate- ECAP refined the grain.79–85
rial. Limited wear particles were seen parallel to the slip Figure 14(a) shows wear behaviour of the samples
direction. It was concluded that machining with ECAE subjected to ECAP process according to the number of
increased the mechanical and wear characteristics of Al ECAP or ECAP temperature. As seen in the figure, the
5083 alloy. The improvement in mechanical and wear wear resistance of the material increased as the number
Güler et al. 15

Figure 13. Optic and SEM Images of The Wear Surfaces of a) N0, b) N1, c) N4, d) N5 samples.

of ECAP increased. The increase in hardness values strength to increase. Another striking point here is the
indicated the increase in the wear resistance and this sample N10. The sample N10 is the sample where
was an expected result. The reason is that the increas- ECAP process was conducted at the highest tempera-
ing number of defect in the structure and decreasing ture and as explained in the previous sections, high
grain size with the increasing ECAP process caused the amount of recrystallisation was seen in this sample.
16 Journal of Composite Materials 0(0)

Therefore, as in other mechanical properties, wear did not cause any significant change in the strength,
properties of this sample were weaker compared to an increase of 40% was observed in the strength
the samples in the same group. However, the wear when the rate was increased to 0.3%. Besides, it can
resistance of this sample was higher compared to the be said that there was a decrease of about 50% in the
sample N1. This can be explained as follows: although elongation amount. This can be thought to be caused
the sample N10 was processed at high temperature and by the Al-Graphene interface. Figure 15(b) shows the
recrystallised, the graphenes found as a reinforcing ele- compression test results of the pure Al samples which
ment according to the sample N1 were oriented. Due to are subjected (N4) and not subjected (N0) to ECAP
this orientation, wear resistance was higher than the N1 process. A significant increase occurred in the strength
sample. of the sample with ECAP process. The same is true for
Figure 14(b) shows the effect of the change in gra- N5 and N1 samples with 0.1% graphene reinforcement,
phene rate for the same ECAP conditions on wear as well (Figure 15(c)). ECAP process causes the
properties. As seen in the figure, an increase was strength of the sample to increase significantly. In addi-
observed in the wear strength along with the increasing tion, Figure 15(d) shows the effect of the number of
graphene amount in the ECAP-processed samples. ECAP on strength for the same sample. The samples
Likewise, wear resistance of the 0.2% graphene rein- N5, N8, N9, and N10 were compared. Although there
forced composite subjected to ECAP process was sig- was a slight increase in the strength of the material with
nificantly higher than the sample without ECAP. the increasing number of ECAP, the elongation
Figure 15(a) shows the stress-strain curves obtained decreased significantly. In fact, it can be easily asserted
as a result of the compression test of graphene rein- that even the samples N8 and N9 became very brittle.
forced composites not subjected to ECAP process. As The reason of the increasing strength of the samples N8
seen in the figure, there is an increase in the strength of and N9 is directly related to the increasing number of
Al along with the increasing graphene reinforcement. ECAP. Because the increasing number of ECAP
Although there was no significant decrease in the elon- increases the defect rate in the samples and the grain
gation for the sample with 0.1% graphene reinforce- size. This is a factor increasing the strength. However,
ment, its strength increased by around 20%. rather than the increase in strength, the striking thing is
Although increasing the graphene amount to 0.2% that the samples turned into a brittle state. This is also
related to the number of ECAP and the increasing
number of ECAP caused the cracks starting on the
surface to increase and grow.
Figure 15(e) shows comparatively compression
results of the samples N1 and N10. As can be remem-
bered, the sample N1 is the sample subjected to ECAP
process at 400
C. As can be seen from the figure and as
explained in the previous sections, the sample recrystal-
lized due to the high ECAP temperature and its
strength values decreased to levels close to the sample
N1 that was not subjected to ECAP process.
In conclusion, it was seen that a significant increase
occurred in strength by applying ECAP process to gra-
phene reinforced Al matrix composites. The reason for
this increase can be associated with: 1) Orientation of
Al grains with the ECAP process, 2) Refining of Al
grains, 3) minimizing the fporosities in the structure
caused by powder metallurgy with ECAP, 4)
Orientation of graphene in the matrix in the direction
of ECAP, and 5) Hardening occurring in the
matrix with ECAP. Another striking condition in sam-
ples with ECAP is that although the strength increased
with ECAP, no decrease occurred in ductility at the
same degree. The reason for this situation is believed
to that the ECAP process was carried out at a temper-
Figure 14. Wear values comparison of a) N5, N8, N9, N10 and ature such as 200
C. Equivalent results were found in
b) N2, N4, N5, N6 samples. similar studies.
Güler et al. 17

Figure 15. Stress-strain curves of a) N0-N1-N2-N3, b) N0-N4, c) N1-N5, d) N5-N8-N9, e) N1-N10, graphene reinforced Al
composite with and without ECAP.

Conclusions successfully produced. An increase was observed in

the mechanical properties and electrical conductivity
Graphene nanosheets were successfully produced by of the composite with the increasing graphene
separating graphite into layers by conducting liquid amount. Along with the increasing graphene amount,
phase exfoliation process, The produced graphene an increase was observed in the microhardness and
was successfully reinforced into the aluminium matrix macrohardness values of the composites and wear
at the rates of 0.1%, 0.2% and 0.3%. The SEM exami- resistance increased and the compression strength
nations revealed that the graphenes were homoge- increased, as well. ECAP process was applied to all
neously distributed into Al and the composite was produced samples. The samples successfully obtained
18 Journal of Composite Materials 0(0)

as a result of the ECAP process were pure Al, 0.1% 7. Wang K, Wang Y, Fan Z, et al. Preparation of graphene
reinforced Al and 0.2% reinforced Al. Al composites nanosheet/alumina composites by spark plasma sintering.
with 0.3% reinforcement broke during ECAP process Mater Res Bull 2011; 46: 315–318.
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Declaration of Conflicting Interests 15. Sutter P. How silicon leaves the scene. Nature Mater
The author(s) declared no potential conflicts of interest with 2009; 8: 171–172.
respect to the research, authorship, and/or publication of this 16. De Arco LG, et al. Synthesis, transfer, and devices of
article. single-and few-layer graphene by chemical vapor deposi-
tion. IEEE Trans Nanotechnol 2009; 8: 135–138.
Funding € Güler SH, Selen V, et al. Production of gra-
17. Güler O,
The author(s) disclosed receipt of the following financial sup- phene layer by liquid-phase exfoliation with low sonica-
port for the research, authorship, and/or publication of this tion power and sonication time from synthesized
article: The authors would like to acknowledge for the finan- expanded graphite. Fullerenes, Nanotubes Carbon
cial support of The Scientific And Technological Research Nanostruct 2016; 24: 123–127.
Council Of Turkey (TUBITAK) (Project No 218M235). 18. Toh SY, Loh KS, Kamarudin SK, et al. Graphene pro-
duction via electrochemical reduction of graphene oxide:
ORCID iD synthesis and characterisation. Chem Eng J 2014; 251:
€ 422–434.
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